Bluish-black azo dye.



Unrrnn smarts PATENT OFFICE.

I osoAR DRESSEL, OF ELBERFELD, AND RICHARD KOlHE, or VOHWINKEL, NEARELBER- FR D, GERMANY, ASSIGNORS TO FARBENFABRIKEN voRM. FRIEDR. BAYER. &00., or, ELBERFELD, G RMAN a CORPORATION or GERMANY.

BLUISH-BLACK AZ O DYE.

" Specification of Letters Patent.

Patented July 16, 1907.

To all whom it, may concern:

Be it-known that WG, OSCAR D'Rnsssnand RICHARD Korma, doctors ofphilosophy, chemists, citizens of the German Empire, residing at,respectively, Elberield and Vohwinkel, near Elberield, in the Kingdom ofPrussia, German Empire, have invented new and useiul Improvements inBluish-Black Azo Dyes,oi which the followin is a specification.

Our invention relates to the manufacture and pro duction of newbluish-black azo dyestuffs containing once or severaltimes the glycinradical I The processfor their production consists in combining thetetrazo compound ofthe dyestuff:para-aminobenzene-azo-2-amino5'naphthol-T-sulionic acid either with twomolecules of an 2.20 dyestuff component containing the glycin radical(NHCH -OOOH) or with one molecule of such a compound and one mole-' culeof any other azo dyestufi component, or vice versa or in converting intothe monodiazo compound the dis azo dyestuff h 1azo-2-amino-5-naphthol-T-sulfonic acid para-p eny ene (X meaning an azodyestul'f component which may or may not contain the glycin radical) andcombining the diazo compound thus obtained either with an azo dyestuffcomponent containing the glycin radical or. if X already contains thisradical, with any azo dyestuff component.

In order to carry out this process one can a. g. ,pro; coed as follows.The tetrazo compound ofparaaminobenzene-azo-2-amino-5-naphthol-7-sulionic acid is combinedeither with two molecules of meta-aminoplienylglycin or with twomolecules of meta-aminotolylglycin NH, 0 n Nn-cH,---ooon;,

or with one molecule of one of these compounds and one molecule ofmeta-phenylenediamin or meta-toluylenediamin, or vice versa.

Analogous coloring matters are obtained if in the preceding examplephenylenediamin or meta-toluylenediamin are replaced by another azodyestui'f component, such as, 2-auiino-S-naphthol-G-sulfonic acid j/2-amino-5-naplithol-7-sulionic acid, l-(ior l 7-naphthylamin sulfonicacid, substitution products of these compounds, naphthol sulfonic acids,resorcinol, aminophenols, etc. etc.

Dyestuffs of analogous dyeihg properties can also be obtained oncarrying out the combination of the above components in any other orderof succession e. g. on

combining the diazo compound of para-aminobcnzene 1.6-naphthylaminsulfonic acid with one molecule of i 2amino-5-naphthol-7-suiforiic acid,diazotizing the col-1 oring matter with one molecule of nitrite andcombining the diazo compound with meta-aminophenylglycin ormeta-aminotolylglycin etc. etc.

Instead of metaaminophenylglycin or meta-amino- V V tolylglycin othersuitable compounds containing the glycin radical can be employed, suchas, glycins of amino-naphthol-sulfonic acids, naphthylamin sulionicacids, or the like.

The new dyestuffs are dark powders easily soluble in.

water and dye full bluish-black shades. Their great I I affinity for thevegetable fiber permits an important simplification inthe dyeing ofhalf-woolen goods as it is possible to dye the cotton fiber of suchfabrics during the milling process full shades, the wool being scarcelytinged at all.

caustic soda lye. The monoazodyestuff thus produced hav ng the formula:

is then ti traotized by means of 14 parts of sodium nitrite and thenecessary quantity of H01 and the tetrazocompound -thus prepared ismixed with an aqueous solution of 16.6 parts of meta-aminophenylglycin.Sodium acetate is added to neutralize the free mineral acid. Theintermediate compound which forms at once is mixed with 33 parts of2-paratolylamino-5- naphthol-7-sulionic acid dissolved in watercontaining Upon reduction with stannous J chlorid and hydrochloric acidthe new dyestuffs are decomposed paraphenylenediamin and 2.6-diamin0-'fi-naphtholJ-sulionic acid being two of the products out), filtered offwarm w E an excess of sodium carbonate. The mixture is stirred forseveral hours, the dyestutt is (if necessary salted and dried. It dyescotton deep blueblack.

In the-iollowing table the shades of some of the new-- dyestuffs aregivenzenediamin +31 mol. Z-amin nap ithol-7- Dyes cotton sulfonicfueid(tetmzotized) 1) 2 mol. mete-amino henylglycin Blue-block.

2; 211101. meta-amino ol lglycin Blue-black.

3 ign ol. meta-aminoplzenylglycin 1 Blue-black.

- metahenylenediamm,

' 4) l mo .meta-toluylenediamin 1 mol. meta- Blue-black.

. aminotolylglycin,

5 1 mol. metekaminophenglaglycin -l- 1 mol. 1- Blue-black.

acetylamino-2A-diamino zeno,

6) 1 mo1. meta-aminophenylglycin e1 mol. Blue-black with meta-aminohenoi, aviolet cast.

7) 1 mol. me a-aminophenylglycin 1 mol.

resorcinol,

Greenish b l u e 8) 1 mol. meta amino lac henylgl cin 1 mol. 1- Greenishbluensphthylamin-tbsul onic aci blac 9) 1 mol. l-naphthylamin-S-suifonicacid 1 Blue-black.

mol. metarnminotolylgiycin,

l0) 1 mol. giycin of the l-na hthylamin-G-sul- Greenish bluefonic aci 1mol. metmp cnylencdiamin, lac v 11) 1 mol. meta-aminophenylglgcin i mol.Blue-black.

l-naphthylemin-7-suifonie aci 12) 1 mol. meta-toluylenedinmin 1 mol.glycin Blue-black.

of the l-naphthylamin-T-sulionic acid, 13) 1 mol. meta-aminophenylglycin1 mol.

l-naphthoi-fi-sulfonic acid,

Greenish blueblack 14) 1 mol. meta-amino;hcuylglycin +-l mol.

Blue-black with 2-aminm5-naphthol-7-suifonie acid, a violet cast. 15) 1mol. meta-airline henylgl cin 1 mol. Blue-black withZ-ethylemino-S-napht oi-7-su onic acid, a violet cast. 1 mol.meta-aminoghcnylglycin 1 mol. Blue-black. 2-diethylamino-5-nathol-7-sul1cnic acid, 17) 1 mol. meta-pheny enediu-min 1 mol. giy-Blue-black.

cin of the 2-am1no-5-naphthol-7-siiiionic acid, 18) 1 mol.meta-aminophenylglycin 1 mol. Blue-black withz-phenylnrnino-5-nnphthol-7-sulfonio acid a. violet cast. 19) 1 mol.msta-aminophenyl lycin 1 mol. Blue-bla,'ck. -2-pa.ratolylamh1o-5-naphtho -7-sul.fonic acid,

) 1 mol. meta-aminotolylglycin 1 moi. 2- Greenishblueanrino-tl-naphthol-G-auifomc acid, 1" black.

1 Idol. meta-phenylenediamin 1 mol. gly- Blue-black.

cin of the Z-amino-S-naphthol-G-sulfonic acid,

'Dy es tufl obtained iromti mol. parahenyh i '50 enediamin 1 mol.Q-amino-5-nsp thoi-7- Dyes cotton sultonlc acid (tetrezotized) i 1 j 22111101. meta-aminophenylglycln 1 mo]. Blue-black i r zr-phenlamino-S-naphthol-(i-mll'onic sci H I" Dyestu obtained from: 23) 1 mol.ace i-lparal-phan lenediamin 1 Blue-black. mol. l-naphtyamin-(i-sufionic acid ithe I acetyl groug being lsFlit o? lmol. 2-amnoa 5-naphthol- -sulio c aci 1 mol. m'etaaminophenylslycln, i 24) 1 mol.ace 1- ara-phen lenediamin 1 Blue-black with mol. l-napht yamin-oonicacid (the aiyioletcast. acetyl groupbelngs lit ofl') +1mol.2-em1no- A5-naphthol-7-sulio 0 acid +1 mol. meta,- I m aminotolylglycin.

Having now particularly described our invention'- 7? and in what mannerthe same is to be performed, what. we claim as new, and desire to secureby Letters Patent; is:- The herein-described azo dyestufls-characterizedby the glycin radical 'NII CII COOH, which dyestutts cn'n be obtained bycombining the tetrazo compound of the dyestuff para nminobenzene nzo2-11mino-S-naphtirolfl-sub tonic acid with two molecules at azo dyestui!components, of which at least one must contain the glycin radical, whichdyestuffs are in the shape of their alkaline salts dark powders easilysoluble in water; dyeing unmordamtedcotton bluish'biack shades nud beingdecomposed byfre duction with ,stnnnous chlorld and hydrochloric field,-pnrapbcnyienediamin and 2.ti -dinmino-,5 naphthoi-7 sulfouic acid beingtwo ofthe products which are formed. substantially as described.

in testimony whereof we have in the presence of twosubscribingwitnesses.

hereuntoset our hands

